Alignment of ferroelectric liquid crystal devices

ABSTRACT

A liquid crystal device comprises a liquid crystal cell including a layer of ferroelectric smectic liquid crystal material contained between two walls bearing electrodes and surface treated to give both an alignment and a surface tilt to liquid crystal molecules. The material adopts a C 2  rather than a C 1  arrangement by arranging the surface pretilt ξ and the ratio of azimuthal to zenithal anchoring energies β/α to give a positive energy difference ΔW s  for the liquid crystal director at the surface in the C 1  and C 2  states. Additionally the provision of a C 2  state may be enhanced by allowing the cell to cool from the isotropic phase to a temperature just below a smectic A to chiral smectic phase, then applying 50 Hz ac voltage in the range typically 0.1 to 5 volts rms. across the liquid crystal layer for about 90 seconds, then allowing the cell to cool to ambient temperature.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to the alignment of ferro electric liquid crystal display (FLCD) devices.

2. Discussion of Prior Art

Such devices are formed by a thin layer of a chiral smectic liquid crystal material contained between two cell walls. The walls carry electrode structures, e.g. row and column electrodes forming an x,y matrix of addressable pixels. Electrical voltages are applied to the row and column electrodes in sequence so that all pixels are addressed in sequence. Prior to assembly, one or both of the inner faces of the cell wall are treated to an alignment treatment that provides both alignment direction and an amount of surface tilt to contacting liquid crystal material. Typical chiral tilted smectic materials have the following phases with decreasing temperature:—isotropic-cholesteric-smectic A-S*, where the asterisk denotes chirality and the smectic phase is tilted smectic such as smectic C, smectic I, etc.

One known type of FLCD is a surface stabilised (SSFLCD) device which is a bistable device. Switching between its two stable states is by application of a dc pulse of appropriate sign, amplitude, and time duration. Smectic liquid crystal molecules can be envisaged as rotating around the surface of a cone as they switch; the cone angle varies with material. Some devices show a minimum in their voltage vs. time switching characteristics (so called τv minimum). Such a device and a typical addressing scheme is described in GB-2,232,802.

It is known that FLCD can show a patchy appearance due to the smectic liquid crystal materials forming into a mixture of two different micro layer arrangements known as the C₁ and C₂ states (ref. J. Kanbe et al Ferroelectrics (1991) vol 114, pp 3). These micro layers are chevron shape and the angle between cell wall and micro layer tilt angle can be indicated by δ. Both C₁ and C₂ can form as the material cools down from an isotropic state during manufacture; boundaries between these two states may be indicated by the known zigzag defect. Also, the two different states may form in a completed device, due to shock, e.g. mechanical damage when dropped or by application of too high an electric field etc.

Devices with a single state are required; preferably alignment in the C₂ state is obtained since this allows a faster switching at lower voltages. It has been a problem for several years to provide a clear, defect free device. Existing solutions include devices where only the C₁ state occurs as in U.S. Pat. No. 5,543,943 Hanyu et al. It is also known to use a high surface tilt ξ GB-2,210469, U.S. Pat. No. 4,977,264, to provide a device free of zigzag defects. GB-A-2,274,519 describes selection of a C₂ state by a surface pretilt ξ equal to or greater than 10°, a chevron angle ξ in the range 2° to 15°, a one half chiral smectic cone angle θ_(c,) such that θ_(c)−δ≧ξ.

Good and consistent alignment is necessary for good devices. There are several ways of providing alignment. For example the walls may be coated with a polymer then unidirectionally rubbed, silicon oxide may be evaporated on to the cell (the so called oblique evaporation technique), and grating surfaces (formed by embossing or by photolithographic techniques). Such alignment treatment both give an alignment direction and a surface tilt to liquid crystal molecules in contact with the treated surface; this may be termed a surface alignment induced pretilt and given the symbol ξ; conventionally the pretilt is measured in a nematic phase. It is known to use long pitch in a cholesteric phase above the smectic phase e.g. GB-2,209,610, U.S. Pat. No. 5,061,047, GB-2,210,468B to improve alignment in the chiral smectic phase.

SUMMARY OF THE INVENTION

According to this invention the above problem is alleviated by a combination of material characteristics, surface alignment induced pretilt and alignment anchoring energy. Additionally, a voltage may be applied to the cell whilst the material is held at a reasonably constant temperature at or below a phase transition to a chiral smectic phase and above a device operating temperature range.

According to this invention a liquid crystal device comprises;

a liquid crystal cell including a layer of ferroelectric smectic liquid crystal material contained between two walls bearing electrodes and surface treated to give both an alignment and a surface tilt to liquid crystal molecules;

the surface pretilt ξ is equal to or greater than θ−|δ| over a device operating temperature range, a ratio of azimuthal to zenithal anchoring energies β/α of at least 0.05 and a positive energy difference ΔW_(s) between the liquid crystal director at the surface in the C₁ and C₂ states the arrangement of angles and energies being arranged to cooperate so that the liquid crystal material preferentially adopts the C₂ state at device operating temperatures.

This may be achieved by careful control of the surface alignment properties by suitable election of material, rubbing strength, and baking temperatures. For example β is high on surfaces that have been strongly rubbed (pressure and time), whereas α may be varied by choice of polymers (and possibly surfactants) to give the required surface free energy. The ration β/α may be higher than 0.05, e.g. 0.1 or more.

The smectic layers form the C2 chevron geometry in which the component of the layer normal at each surface which is parallel to the surface normal has opposite sign to the component of the liquid crystal molecular director n at the pretilt and in the preferred alignment direction.

This is achieved by ensuring that the pretilt ξ is close to θ−|δ| (where θ is the smectic C cone angle and δ is the smectic layer tilt angle) at some temperature (T₂) in the smectic C phase above an operating range (e.g. −10 to 60°, preferably 0 to 40° C.) and uniformly throughout the device. Preferrably ξ≧θ−|δ| within about 5° of smectic phase transition T₁.

Having obtained the desired C2 state it is maintained by ensuring ξ≧θ−|δ|, preferably ξ>θ−|δ|, across the temperature range for operation.

Preferably ΔW_(s) and the ratio β/α are as large as possible. For a given value of β/α, the pretilt ξ is optimised to give ΔW_(s) positive and as large as possible across a temperature range of operation. Preferably the material changes from a C₁ state to a C₂ as close to a smectic A to a chiral smectic phase transition (T₁) as possible, e.g. within 10° C. or less.

The device may further comprise means for applying voltages to row and column electrodes in the cell whereby the complete device may be addressed.

The device may further include means for heating the cell, allowing the cell to cool a predetermined temperature, and means for applying an ac voltage across the liquid crystal layer for a predetermined time. After the heating, the cell may then be cooled to ambient at a controlled rate. Such treatment may be performed to remove damage to alignment within the cell, e.g. caused by impact or other mishap subsequent to device manufacture.

According to this invention a method of making a ferroelectric liquid crystal device comprises the steps of:

providing a liquid crystal cell having a layer of a chiral smectic liquid crystal material contained between two cell walls bearing electrodes and surface treated to provide both an alignment direction and a surface pretilt to liquid crystal molecules;

providing a surface treatment giving a pretilt ξ and a ratio of azimuthal to zenithal anchoring energies β/α which gives a positive energy difference ΔW_(s) between the liquid crystal director at the surface in the C₁ and C₂ states whereby the liquid crystal material preferentially adopts the C₂ state at device operating temperatures;

heating the liquid crystal material to a phase above a smectic phase and introducing the liquid crystal material between the cell walls;

cooling the liquid crystal material to around or just below the phase transition to a chiral smectic phase,

applying an ac voltage across the liquid crystal layer sufficient to cause formation of a C₂ structure without causing formation of quasi bookshelf layer configuration,

removing the voltage and cooling the liquid crystal material down to ambient temperature.

The voltage may be an ac voltage of between 0.1 to 10 volts, typically 2 volts, at a frequency of between 1 to 500 Hz typically 50 Hz.

The application of the voltage at the phase transition may be at the time of initial introduction of the liquid crystal material between the cell walls, or at a later time. In the later case the material will be reheated up to above the smectic phase and cooled in two stages with an intermediate application of voltage as above. Such an action may also be employed to repair cells damaged e.g. by shock or vibration, or over heating, or electrical damage. The step of finally sealing the liquid crystal material between the walls may be after the material has cooled down to ambient temperature.

The application of an ac voltage may be at a temperature just below the phase transition or within a few degrees below the transition depending upon the material; e.g. within 10° preferably less than 5° below the transition.

Additionally, and/or instead of the applied ac voltage, pressure and/or vibration may be applied to the cell at around the T₂ temperature. The effect of ac voltage, pressure, and vibration may be to cause movement within the layer so that the preferred lower energy C₂ state is obtained at the lower temperatures of the device operating range.

The liquid crystal material may be a chiral smectic material such as smectic C, I, H, etc. or antiferro electric materials, and may have the following phases with decreasing temperatures:

isotropic-cholesteric-smectic A-chiral smectic-(with or without additional higher order smectic phase(s))—solid.

The material in the cholesteric phase may be a compensated material with a long pitch just above the cholesteric to smectic phase transition. Such a material is described in GB-2,209,610, U.S. Pat. No. 5,061,047. For some materials the cholesteric or the smectic A phase may be missing.

BRIEF DESCRIPTION OF DRAWINGS

The invention will now be described, by way of example only with reference to the accompanying drawings of which:

FIG. 1 is a diagrammatic view of an x,y display with row and column drivers;

FIG. 2 is a cross section of the display cell of FIG. 1;

FIG. 3 is a schematic view of a layer of ferroelectric liquid crystal material, showing two alignment configurations, the C₁ and the C₂ states;

FIG. 4 is a schematic view showing movement of a liquid crystal director around the surface of a cone as the director is switched by application of a suitable voltage-time product;

FIGS. 5, 6, and 7 show energy plots against micro layer tilt δ, indicating relative positions of the two states C₁ and C₂;

FIG. 8 is a plot showing how the C₁ and C₂ states are favoured at different temperatures for one value of surface pretilt ξ;

FIG. 9 is a plot of surface energy difference ΔW_(s) between the C₂ and C₁ states against the surface anchoring energy ratio β/α for different surface pretilts ξ where β is the aximuthal anchoring energy and α the zenithal anchoring energy;

FIGS. 10, 11 are plots showing the difference in surface energy ΔW_(s) between C₂ and C₁ against surface pretilt ξ for one material with different values of β/α at two different micro layer angles δ;

FIG. 12 is a graph showing how smectic cone angle θ, and micro layer tilt angle δ varying with temperature for a typical material when the surface pretilt ξ remains at a constant value;

FIGS. 13a, b, show how the value of micro layer tilt angle δ in FIG. 12 may be altered by application of an ac voltage to enhance change of material from the C₁ to the C₂ state;

FIG. 14 shows how the value of surface pretilt ξ may be varied with temperature, compared with a θ−|α| curve;

FIG. 15 shows variation of micro layer tilt angle δ against temperature for a device where δ is low just below a smectic phase transition, increasing thereafter with decreasing temperature, the value of θ is also show and is similar to that in FIGS. 12, 13;

FIG. 16 is a plot of surface energy ΔW_(s) against micro layer tilt δ for different values of β/α;

FIG. 17 is a graph of log time of applied voltage pulse against log voltage applied, showing the switching characteristics of a typical FLC smectic liquid crystal material operating in a τV_(min) mode;

FIG. 18 shows data, and strobe, waveforms for applying to the display of FIG. 1 to address the display;

FIG. 19 shows resultant waveforms for applying to the display of FIG. 1 to address the display;

FIG. 20 is a graph of angle against temperature a range over which a C₂ can be achieved, and a curve showing pretilt angle ξ at which ΔW_(s) is most positive (and hence C₂ most stable) for the ratio β/α≧0.05; and

FIG. 21 is a graph of angle against temperature showing a constant pretilt ξ, and different values of θ−|δ| obtained by application of an ac voltage.

DETAILED DESCRIPTION OF INVENTION

The display cell 1 shown in FIGS. 1, 2 comprises two glass walls 2, 3 spaced about 1-6 μm apart by a spacer ring 4 and/or distributed spacers.

Electrode structures 5, 6 of transparent tin oxide are formed on the inner face of both walls. These electrodes are shown as row and column forming an X, Y matrix but may be of other forms. For example, radial and curved shape for a polar co-ordinate display, or of segments form for a digital seven bar display, or plain sheet electrodes to form an optical shutter.

A layer 7 of liquid crystal material is contained between the walls 2, 3 and spacer ring 4.

Polarisers 8, 9 are arranged in front of and behind the cell 1. Row 10 and column 11 drivers apply voltage signals to the cell. Two sets of waveforms are generated for supplying the row and column drivers 10, 11. A strobe waveform generator 12 supplies row waveforms, and a data waveform generator 13 supplies ON and OFF waveforms to the column drivers 11. Overall control of timing and display format is controlled by a control logic unit 14.

Prior to assembly, the walls 2, 3 are surface treated by spinning on a thin layer of polymeric material such as polyimide or polyamide, drying and where appropriate curing; then buffing with a soft cloth (e.g. rayon) in a single direction R₁, R₂. This known treatment provides a surface alignment for liquid crystal molecules. In the nematic and cholesteric phases and in the absence of an applied electric field the molecules at the surface walls 2, 3 align themselves along the rubbing direction R₁, R₂ and at a pretilt angle ξ of about e.g. 2° to 10° to the surface as described more fully below.

The rubbing directions R₁, R₂ are substantially parallel and in the same direction (for some devices R₁ and R₂ may be some degrees away from parallel). The sample is aligned by cooling through the higher temperature phases to the required ferroelectric phase. When suitable unidirectional voltages are applied the molecules (more corectly the director n) in the bulk of the material tend to align along one of two directions D₁, D₂ depending on polarity of the voltage. Typically the angle between D₁, D₂ is about 45°, but varies with material and the amount of ac bias applied during addressing.

The surface alignment treatment is arranged to provide the required value of pretilt ξ, for reasons discussed in more detail later. The material polyimide (e.g. Polyimide 32) when rubbed gives a typical pretilt of about 2°; the actual value depends upon liquid crystal material and the processing. Alternatively, as described in GB-A-2,286; GB-A-2,286,467; GB-A-2,286,894; GB-A-2,2986,893, the cell walls may have formed thereon grating structures which provide a range of pretilt angles and alignment directions. The granting may be symmetric and/or asymmertric in profile, and shaped to give any desired value of pretilt ξ, and azimuthal and zenithal anchoring energies β, α respectively.

The device may operate in a transmissive or reflective mode. In the former light passing through the device e.g. from a tungsten bulb 15 is selectively transmitted or blocked to form the desired display. In the reflective mode a mirror 16 is placed behind the second polariser 9 to reflect ambient light back through the cell 1 and two polarisers. By making the mirror 16 partly reflecting the device may be operated both in a transmissive and reflective mode.

Pleochroic dyes may be added to the material 7. In this case only one polariser is needed and the layer thickness may typically be 4-10 μm.

On manufacture, a liquid crystal cell 1 is filled with the material 7 heated to its isotropic phase, and drawn in by capillary attraction in a conventional manner. The cell may be subjected to an applied voltage as follows. The cell is then allowed to cool, e.g. at between 0.1 to 1.0° C. per minute, from the isotropic phase until just below the smectic A to chiral smectic phase. The cell is kept at this temperature for about 20 to 120 typically 60 seconds whilst an ac voltage of typically between 0.5 and 5.0 volts e.g. 2 volts (rms.) at 1 to 500 Hz e.g. 50 Hz. The voltage is then removed and the cooling continued. Upon removal of the voltage the cell adopts the C₂ state, as described below.

As the material cools the molecules form into micro layers 20 which may be bent as shown in FIG. 3. Two possible different arrangement of bent layers can form and are given the known descriptors C₁ and C₂. In many cells both C₁ and C₂ can occur in different parts of the cell; they appear visibly different thereby degrading device appearance.

Molecules (i.e. the director n) 21 tend to lie as if on the surface of a cone 22, seen more clearly at FIG. 4. Adjacent the cell walls 2, 3 strong aligning forces anchor the molecules 21 in a tilted and aligned direction, away from the walls the molecules tend to arrange themselves as shown in one of two stable positions on the cone approximately in the plane of the layer 7. When a dc electric field of appropriate polarity amplitude and time is applied there is a coupling between the molecule and the field and the molecules 21 rotate around the cone 22 from one switched position (shown in solid lines) to the other switched position (shown in broken lines), i.e. maximum rotation in the plane of the layer 7 is twice cone angle (2θ).

The angle of the cone 22 around which the molecule 21 rotate is the cone angle θ, the angle between a cell wall 2, 3 normal and a micro layer 20 is herein defined as δ, the angle of molecules at a cell wall is herein defined as the surface tilt or pretilt angle ξ. Note, the pretilt angle ξ (in the e.g. rubbing direction R) provided by the surface alignment is slightly different than the surface angle when in a cell and lying on the surface of the cone 22 (and to one side of the e.g. rubbing direction R). The energy required by molecules to adopt a particular arrangement depends upon material characteristics and the surface treatment applied to the cell walls. This is explained in part in the FIGS. 5-12 as follows.

FIG. 5 shows a plot of energy against micro layer angle δ for a cell where surface pretilt ξ is zero. Two equal energy minima occur at δ≅+/−δ₀ corresponding to the C₁ and C₂ states. Between these minimum values is a barrier of ΔE1. When a liquid crystal material is cooled, the material may adopt one or both of these C₁ and C₂ states because they are equally favoured as far as energy levels are concerned in some devices.

FIG. 6 is similar to FIG. 5 but the energy level for state C₁ is lower than for C₂. Therefore state C₁ will be favoured on cooling. This will occur just below a smectic A to chiral smectic phase transition where ξ>>θ−|δ| and ξ≦θ+|δ| as explained with reference to FIG. 8 below.

FIG. 7 is similar to FIG. 5 but the energy level for state C₂ is lower than for C₁. When ξ>θ−|δ|, state C₂ will be favoured on cooling.

The present invention provides a cell where state C₂ will be favoured on cooling. This is achieved by use of materials with the desired characteristics, surface tilt treatment. Additionally an ac electric potential may be applied across the layer 7 during device manufacture.

FIG. 8 shows how the characteristic θ−|δ| and θ+|δ| varies with temperature for a typical material in a typical prior art cell. For simplicity it is assumed that the surface pretilt is ξ and does not vary although as in the present invention surfaces may be chosen where this is not the case. The material has a smectic A phase immediately above the chiral smectic phase S_(C)*. Immediately below the phase transition T₁, the values of ξ−(θ−|δ|) are positive and a C₁ state forms which remains until ξ≈θ−|δ| at a temperature of T₂. Below this temperature T₂ ξ<θ−|δ| and the C₂ state preferentially forms.

In conventional devices to provide a C₂ state the surface tilt ξ is arranged to be close to θ−|δ| at ambient temperature. Unfortunately, for typical devices this requires a low value of surface tilt ξ, and leads to the co existence of C₁ and C₂ states. In GB-2,274,519-A, the C₂ state is obtained by application of a low frequency and low voltage AC waveform to the device. The effect of the waveform is to change the chevron angle δ and allow the material to change from C₁ to C₂ states when high (e.g. greater than 10°) surface tilt ξ angles are used.

To provide the desired C₂ state the C₂ energy state must be lower than that of the C₁ state, i.e. ΔW_(s) is positive and the energy barrier ΔE₁ (FIG. 5) between the two levels must be low enough to allow any part of the material in a C₁ state to change to the C₂ state. This achieved by a combination of the surface tilt ξ, the ratio β/α, at working ambient temperatures, and the temperature during formation of the C₂ chevron structure.

Conventionally to obtain a C₂ state ξ₀<θ−|δ₀| (below the bottom curve in FIG. 20), and so the maximum value of ΔW_(s) would be expected to be less than 3° for FIG. 10 and less than 6° for FIG. 11. In FIG. 10 (where θ−|δ₀|=3°) the maximum ΔW_(s) occurs at about 6° with a β/α ratio of 0.2; in FIG. 11 (where θ−|δ₀|=6°) the maximum ΔW_(s) occurs at about 8° with β/α ratio of 0.2. However, this shows ΔW_(s) maximum when in the C₂ state. What must also be considered is the ability of the material to adopt the C₂ state on cooling and at a temperature well above the operating range.

Ideally, the C₂ state should form spontaneously on cooling at some temperature well above the desired operating range and close to the transition temperature T₂, for example within 5° of the phase transition. At this phase transition the material is more mobile and can change from the C₁ state to the C₂ more readily than at lower temperatures.

Part of the reason for this mobility is that the energy barrier ΔE₁ (FIG. 5) between the two states varies with temperature. At temperatures close to the phase transition T₁, the energy barrier is low and increases with decreasing temperatures. Therefore transition to a C₂ state in enhanced by a low ΔE₁ and large positive values of ΔW_(s) just below T₁. Across the operating temperature range (well below T₂) it is required that the energy difference ΔW_(s) is positive and as high as possible so that the sample is uniformly C₂ across the device, despite irregularities which may occur due to surface variations, the spacers, electrode edges etc. Thus in an operating temperature range, the state C₂ will be retained even though ξ₀>θ−|δ₀|.

As shown in FIG. 10, ΔW_(s) is maximised with a high β/α, and a pretilt of about 6° which is substantially above ξ=θ−|δ|=3°. However, as seen in FIG. 8, close to the smectic C* to smectic A phase transition at T₁, θ−|δ| is low for typical materials, growing continuously from zero at the phase transition at T₁. Thus, (since θ−|δ| is less than ξ just below T₂), C₁ always forms first, and the C₂ state may become favourable at some lower temperature (as θ−|δ| becomes greater than ξ). Therefore increasing ξ (as shown in FIGS. 10, 11 to maximise ΔW_(S) in the C₂ state) will reduce the ability of the material near the transition T₁ to change from C₁ to C₂ (FIG. 8), and lower the T₂ value towards the device operating range.

There is therefore a conflict between the requirements to obtain a maximum ΔW_(s) in a range of operating temperature and to obtain a change of state from C₁ to C₂ just below the phase transition at T₁.

At operative temperatures material properties are “fixed”, e.g. θ≈22°, and δ≈19°. The ratio β/α should be as high as possible but this is difficult to control and is typically about 0.2. FIG. 10 shows that optimum pretilt is high and about 6°. Thus pretilt of ξ=6° is needed to get a uniform and stable C₂ state across a device operating temperature range. However, on cooling, it is necessary to get into the C₂ state close to the phase transition T₂ where change in alignment will be easy and so that C₂ occurs across a maximum temperature range. With conventional materials and surface pretilt of ξ=6° and β/α=0.2 will not go into the C₂ state close to the transition since pretilt ξ>>θ−|δ|. Therefore is necessary to increase θ−|δ| through change in micro layer tilt δ (e.g. by use of voltage and/or special material) close to the transition T₂, or make the pretilt ξ lower just below the transition T₂, but higher in the device operating temperatures.

Preferably the value of θ−|δ| close to the phase transition temperature T₁ is deliberately made closer to the pretilt ξ value (or visa versa), thereby enabling the C₁ to C₂ alignment transition to occur, preferrably as close to T₁ as possible. Once this is achieved, the values of θ−|δ| may be allowed to increase as the temperature decreases, to be the same as in conventional devices or even higher, and the pretilt much higher than previously used. Hence a more uniform and stable C₂ state is achieved.

This is explained with reference to FIG. 12 which is a plot of angle against temperature showing how θ varies from zero at the smectic A to smectic C* transition at T₁ to e.g. 25° at ambient temperature for a typical device. Also shown is a plot of δ which is normally a constant fraction of θ, (e.g. δ≅0.85θ). Ideally δ should vary just below T₂ and may be achieved in several ways. For example:

(1). Apply a voltage across the liquid crystal layer 7 whilst the material is at a temperature immediately below the transition temperature T₁ to lower the layer tilt angle δ, thereby increasing θ−|δ| towards ξ This is shown in FIG. 13 where the value of δ decreases substantially as a voltage is applied at T₂.

(2). Use surface alignment treatment and liquid crystal materials with a temperature dependent pretilt so that ξ low (i.e. ξ≈θ−|δ|) close to the phase transition at T₁ but ξ is higher across the operating temperature range below T₂. This is shown in FIG. 14 where ξ increases gradually as the temperature drops to T₂, then increases rapidly on further cooling. An example of such a surface alignment treatment is described by V. N. Raja et al (1996) MLCC 287, pp 169-175, which uses a rubbed surface of a liquid crystal polymer LCP100 (available from E Merck)

Surface director interaction can be explained as follows (Ferroelectrics, 1996, Vol 178, pp 155-165):

The surface interaction is complicated in the SmC* phase by the effects of the biaxiality and ferroelectricity. For simplicity, a uniaxial nematic-like surface energy, W_(S) is assumed, which has the form:

W _(S)=α(n.s)²+β(n.t)²−γ(n.s)·(n.r)

where s is the surface normal, r is in the plane of the substrate and parallel to the preferred direction of n, and t is defined by r x s, as shown in FIG. 3a. This energy is similar to that used previously but is rewritten in a form so that coefficients α and β correspond to the zenithal and azimuthal anchoring energies, respectively, and γ is related to the pretilt.

In the nematic phase, a director at an in-plane twist angle η and out-of-plane tilt angle ξ has the surface energy:

W _(S)=α sin² ξ+β cos^(2 ξ sin) ² η+γ sin ξ cos ξ cos η

Defining the minimum energy orientation in the (s,r) plane at the pretilt angle ξ_(s) leads to: ${\tan \quad 2\xi_{s}} = {- \frac{\gamma}{\alpha}}$

In the smectic C (*) phase, the director is constrained to lie on a cone, tilted with respect to the surface normal at the layer tilt angle δ, as shown in FIG. 3b. The surface energy is then given by:

W _(S)=α(cos δ sin θ sin φ−sin δ cos θ)²+β sin² θ cos² φ

−γ(cos δ sin θ sin φ−sin δ cos θ)·(sin δ sin θ sin φ+cos δ cos θ)

The energy difference for the liquid crystal director at the surface in the C₁ and C₂ states is defined by:

ΔW _(s) =W _(s)(δ=−δ₀)−W _(s)(δ=+δ₀)

where δ₀ is the characteristic layer tilt for the material at a given temperature. If ΔW_(s) is positive, the C₂ state has a lower surface energy than the C₁ and is therefore more likely to occur.

The above relatively simple arguments need to be modified to take into account the effects of surface alignment induced anchoring energies as follows:

The relationship between ΔW_(s) and the ratio of the azimuthal to zenithal anchoring energies β/α is plotted in FIG. 9 for several values of pretilts ξ. Above the ΔW_(s)=0 line the C₂ state exists and below that line the C₁ state exists. The material was the commercially available Merck material SCE13; at 30° C., δ₀=18.5°, θ=21.75°, and thus θ−|δ₀|=3.25°. FIG. 9 shows that the C₂ state is most stable for 3° (i.e. ξ₀≅θ−|δ₀|) for all values of β/α. and for other surface tilt ξ when combined with high values of β/α. For ξ₀<θ−|δ₀|, e.g. 1°, the C₂ state is always more energetically favourable, but the magnitude of ΔW_(s) is relatively small at low β/α values. For ξ₀>θ−|δ₀|, e.g. 7°, the C₂ state is energetically favourable only for the higher values of β/α. The graph shows that ΔW_(s) can be made highly positive for surface tilts ξ much higher than θ−|δ|. However, if the surface tilt ξ is made too high the C₁ state again becomes more stable, i.e. when ΔW_(s) is negative as explained with FIG. 20 below.

FIG. 10 shows plots of ΔW_(s) against pretilt ξ for varying β/α, when θ=20°, and δ₀=17°, i.e. <θ−|δ₀|=3°. FIG. 11 shows plots of ΔW_(x) against pretilt ξ for varying β/α, when θ=20°, and δ₀=14°, i.e. <θ−|δ₀|=6°. These two FIGS. 10, 11 show how the β/α ratio and surface pretilt ξ may be adjusted to ensure that ΔW_(s) is maximised and the C₂ state favoured.

Variation of ΔW_(s) is shown in FIG. 20 where angle is plotted against temperature. The lower dotted curve shows θ−|δ| variation as in FIG. 8. The upper dotted curve shows the surface tilt ξ limit above which ΔW_(s) is negative and the C₁ state is most stable. The centre solid line curve shows the surface tilt ξ at which ΔW_(s) is most positive and therefore C₂ is most stable, for the ratio β/α°≧0.05. Stable C₂ state operation is therefore obtained with surface tilt ξ between the upper and lower curves. Preferrably ξ has a value which follows the centre solid curve.

(3). Choose FLC materials where θ−|δ| is unusually high close to the phase transition. This is shown in FIG. 15 where δ is small just below the phase transition, and increases together with θ as the temperature drops further.

Having achieved high ΔW_(s), the stability of the layer geometry to electrical, thermal or mechanical disruption is related to the potential barrier ΔE₁ between the C₁ and C₂ states. This should be made high to resist or prevent damage or zero so that if damage occurs the layers relax in the C₂ state spontaneously These requirements for high ΔW_(s) and high potential barrier ΔE₁ between the states require that β/α is high. However, if the potential barrier ΔE₁ is then too high, the material will be “trapped” in the C₁ state and the C₂ state will either not form at all, or will form in patches with zigzag defects across the sample. For this reason, as explained above, the value of ΔE₁ should be large over a device operating range and be low around T₂ .

FIG. 16 shows surface energy against layer tilt ξ for different β/α. The energy minimum for the C₁ state increases with increasing β/α. ratio. Also, the height of the energy barrier ΔE₁ between the two states C₁ , C₂ increases with increasing β/α. These plots are for θ=22.5, δ₀=19°, ξ₀=10°. From this graph, the values of ΔW_(s) and ΔE₁ can be optimised.

EXAMPLES Example 1

A standard polyimide was prepared as follows (PI-32 processing): Cell walls were coated with adhesive promoter (methanol solvent); PI-32 in NMP solution was spundown on the surface; the coated walls were given an initial bake for 10 minutes at 120° C. followed by full baking at 300° C.; the baked surfaces were rubbed hard with a Rayon cloth. A cell was assembled with rubbing direction parallel, and filled with SCE13 (Merck material), cell spacing 1.4 μm. Surface pretilt was found to be approximately 4° (measured conventionally in a nematic phase). The ration of β/α was 0.2 determined by the method of Jones above.

The cell was aligned by cooling at 1° C. minute from its nematic phase through the smectic A phase into the smectic C phase. It was found that the S_(A) to S_(C) transition (to state C₁) started to occur at 58.9° C. and the C₁ state started to form at 52.6° C. The cell was found to have formed approximately 20% C₂ after being cooled to room temperature. The material SCE13 had a value of θ−|δ|≈1.5° at 45° C. and ≈0.5 at 55° C. The values of θ and δ were found using the method of Anderson et al (1991) J. Phy. D Applied Phys 24, pp 338 at different applied switching fields, including zero.

Example 2

The cell was then realigned several times from the nematic but at 57.5° C. the cooling was suspended for 60 seconds whilst a 50 Hz square wave was applied to the cell. Different voltage levels (including zero for comparative purposes) was applied. The application of the voltage was performed at 57.5° C. since this temperature was between the S_(A) to S_(C) * and C₁ to C₂ transitions. Upon application and removal of the voltage C₂ texture could be seen clearly to form over the viewed area of the cell.

It was found that application of no applied voltage led to approximately 20% C₂ texture when cooled to room temperature. The application of 0.5 volts at T₂=50° C. gave about 60% C₂, 1.0 volts gave about 95% C₂, and 2.0 volts gave virtually 100% C₂ (i.e. only a small number of defects at the edge of a 1 cm² test area).+

The field is then removed and the cell cooled below 57.5° C. to an operating temperature of say 25° C.; the optical extinction angle was found to be approximately the same as for an untreated (without an applied voltage at T₂) cell. Hence θ−|δ|≈1.5° which is substantially lower then ξ=3° or 4°. Thus the desired result of about 100% C₂ was obtained with ξ=θ−|δ|. This then gave good switching performance associated with a C₂ state.

It was also found that application of the equivalent DC voltages led to damage textures, as there was a tendency for the layers to become “bookshelf” geometry, but with the layer normal twisted in the plane of the cell.

Variation of parameters for the examples 1, 2 are shown in FIG. 21. Surface tilt ξ is constant at 4° over the shown temperature range. Curve A shows the variation of θ−|δ| with temperature as in FIG. 8 for the material SCE13. Curve B is similar but on cooling down to 57.5° an ac voltage is applied which causes a change in layer tilt δ to about 3°. Curve C is similar but with a much higher applied voltage forcing δ to approach zero. For this curve C defects occurred, associated with a quasi bookshelf type of micro layer configuration.

Example 3

By way of comparison, the previous cell was reheated to the isotropic phase and recooled to the smectic C phase to a temperature of 30° C., whereupon the alignment was predominantly C₁ state. This indicates that the temperature T₂ occurs within the operating range of temperatures and not just below the phase transition T₁.

Application of 50 Hz 20 volts rms. caused significant disruption of the layers. The appearance was patchy and the alignment poor but the cell had undergone considerable “quasi-bookshelf” treatment; extinction angle measurement suggested that many areas gave δ≈12° and the C₂ state did not form.

Further experiments were carried out to measure the effect of applied voltages during a constant temperature. It was found that the values of the τV curve (FIG. 17) was lowered. This means that lower addressing voltages could be used.

The display of FIG. 1 may be addressed in a conventional manner. For example as described in GB-2,232,802B. U.S. Pat. No. 5,398,042. SSFLCDs switch; between two stable states or molecular directions; a positive pulse will switch into one state and a negative pulse switch into the other state. Typical switching characteristics are as shown in FIG. 17; material is switched by time-voltage products above the curve, any time-voltage product below the curve does not switch.

Strobe waveforms, FIG. 18 are applied to each row electrode in turn. The strobe is formed of pulse pairs, a positive pulse followed by a negative pulse to each row, forming a first field of addressing. This is followed by the invert, i.e. a negative pulse then a positive pulse to each row in turn forming a second field. Two fields are required to completely switch all desired pixels. The column electrodes receive one of two data waveforms all the time. The data waveforms are alternate positive and negative pulses, with Data 1 the inverse of Data 2. One data co-operates with one strobe pulse pair to switch in one direction, whilst the other data co-operates with the other strobe pulse pair to switch in the opposite direction.

The four possible resultant waveforms are shown in FIG. 19; strobe and Data 1 switches with a large positive pulse in the second field, whilst strobe and Data 2 switches with a large negative pulse in the first field. Use of two strobe pulse pairs of opposite polarity, and data waveforms of alternate polarity ensures net zero dc across the liquid crystal material. 

What is claimed is:
 1. A liquid crystal device comprising: a liquid crystal cell including a layer of ferroelectric smectic liquid crystal material contained between two walls bearing electrodes and surface treated to give both an alignment and a surface pretilt to liquid crystal molecules; wherein the surface pretilt ξ is equal to or greater than θ−|δ| over a device operating temperature range, a ratio of azumuthal to zenithal anchoring energies β/α of at least 0.05 and a positive energy difference ΔW_(s) between the liquid crystal director at the surface in the C₁ and C₂ states the arrangement of angles and energies being arranged to cooperate so that the liquid crystal material preferentially adopts the C₂ state at device operating temperatures further comprising means for heating the cell, means for allowing the cell to cool at a predetermined rate to a predetermined temperature, means for applying an ac voltage across the liquid crystal layer for a predetermined time, and means for cooling the cell to ambient temperature at a controlled rate.
 2. The device of claim 1 and further comprising means for applying voltages to row and column electrodes in the cell whereby the complete device may be addressed.
 3. The device of claim 1 wherein the ratio of β/α is at least 0.1.
 4. The device of claim 1 wherein the surface pretilt ξ is greater than θ−|δ| over a device operating temperature range.
 5. The device of claim 1 wherein the surface pretilt ξ varies with temperature to give a high value at ambient temperatures and a lower value at higher temperatures near a smectic phase transition.
 6. A method of making a ferroelectric liquid crystal device comprising the steps of: providing a liquid crystal cell having a layer of a chiral smectic liquid crystal material contained between two cell walls bearing electrodes and surface treated to provide both an alignment direction and a surface pretilt to liquid crystal molecules; wherein providing a surface treatment giving a pretilt ξ and a ratio of azumuthal to zenithal anchoring energies β/α which gives a positive energy difference ΔW_(s) between the liquid crystal director at the surface in the C₁ and C₂ states whereby the liquid crystal material preferentially adopts the C₂ state at device operating temperatures; heating the liquid crystal material to a phase above a smectic phase and introducing the liquid crystal material between the cell walls; cooling the liquid crystal material to just below the phase transition to a chiral smectic phase; applying an ac voltage across the liquid crystal layer sufficient to cause formation of a C₂ structure without causing formation of quasi bookshelf layer configuration; removing the voltage and cooling the liquid crystal material down to ambient temperature.
 7. The method of claim 6 wherein the ac voltage is between 0.0833 and 50 volts/μm of layer thickness, and a frequency of between 1 and 500 Hz.
 8. The method of claim 6 wherein the cooling is at a rate of between 0.1 and 50° C. per minute.
 9. The method of claim 6 wherein the ac voltage is applied for a time between 1 and 120 seconds.
 10. The method of claim 6 wherein the ac voltage is applied whilst the liquid crystal material is within the range of the chiral smectic phase transition to about 10° C. below the transition.
 11. The method of claim 6 wherein the liquid crystal material is a chiral smectic C in a range of operating temperatures.
 12. The method of claim 6 wherein the liquid crystal material has the following phases with decreasing temperatures: isotropic-cholesteric-smectic A-chiral smectic-solid.
 13. The method of claim 6 wherein pressure and/or vibration is applied to the liquid crystal layer at a temperature below but within 10° C. of a smectic phase transition. 